Polymeric organopolysiloxanes containing phenylene and silane linked silicon atoms



2,696,480 Patented Dec. 7, 1954 POLYMERIC ORGANOPOLYSILOXANES CON- TAINING PHENYLENE AND SILANE LlNKED SILICON ATOMS Arthur F. Gordon and Harold A. Clark, Midland, Mich., assignors to Dow Corning Corporation, Midland, Mich., a corporation of Michigan No Drawing. Application October 20, 1951, Serial No. 252,431

5 Claims. (Cl. 260-465) The present invention relates to organosiloxane polymers in which the silicon atoms are linked by oxygen atoms, by phenylene radicals, and by silicon to silicon bonding, and to a method for preparing organosiloxane copolymers containing phenylene linked silicon atoms.

The organosiloxane fluids and resins are now well known commercially available products. In such polysiloxanes all of the silicon atoms are connected only by oxygen atoms. Organosilicon resins in which the silicon atoms are connected by phenylene radicals or by substantially only silicon to silicon bonding are also known. Polymeric organosiloxane fluids or resins containing all three of these types of silicon linkages, however, have not been known heretofore.

It is an object of the present invention to provide new and improved organosilicon fluids and resins in which some of the silicon atoms are linked by oxygen atoms, others by phenylene radicals, and others by silicon to silicon bonding, and to provide a method for the preparation of such products; It is a further object to provide a novel method for the preparation of organosiloxane polymers in which the silicon atoms are linked by oxygen atoms and phenylene radicals.

The present invention particularly relates to a process in which an organohalosilane having the general formula RCH3SiX2, an organosiloxane polymer containing polymeric units of the formula and an alkali metal are reacted in liquid phase. In the above formulae R represents a methyl or phenyl radical, X represents a halogen atom, preferably chlorine or bromine, and x is an integer of from 0 to l inclusive. This process results in a product which may be either fluid or resinous in nature, depending upon the reactants and the relative proportions used. 'Iheexact complete structure of the products obtained is not completely understood. It is known, however, that the copolymer products contain SiOSi and SiCsH4Si types of linkages, and under the proper conditions also contain the polysilane Si-Si linkages. The latter copolymers contain units of the general formulae R CaH4|louH4(CH3)zSI03 r CH3 T and R R ilC6H4(CH3)z lO:

z CH3 2 where R is methyl or phenyl and x is 0 or 1. Any other CH3 JHa where R is alkyl, aryl, or halogenated aryl, n is an integer of from 0 to 3 inclusive, and R is methyl or phenyl.

The alkali metal which may be used in this reaction may be any of the Well known alkali metals, such as sodium, potassium, caesium, and rubidium. The sodium potassium eutectic mixture may also be employed. It is preferred, due to commercial availability, however, to employ either sodium or potassium.

The organohalosilanes of the formula RCH3SiX2, where R is methyl or phenyl, are Well known and in the case of the chlorosilanes, commercially available materials.

Polymers containing units of the general formula can be prepared, for example, by the hydrolysis and condensation of XCeH4SiX3 and/or XCsH4CH3SiX2 or by the cohydrolysis and cocondensation of either or both of these materials with other hydrolyzable silanes, thus producing copolymers. When copolymers are prepared, it is preferred that the other hydrolyzable silanes be of the general formula RnSiX4 -n, Where n has an average value of from O to 3 inclusive and R is an alkyl, aryl, or halogenated aryl radical. Preferably, R is a methyl, phenyl, polyhalophenyl, or haloxenyl radical or mixtures of such radicals. The term xeny is used herein to designate the radical CeI-I5CsH4.

Thus, for example, ClCsH4SiCla and/ or ClCsI-I4CHsSiCl2 can be cohydrolyzed with CHsSiClz, (CHs)2SiCl2, (CH3)3SiCl, C(iH5SlCl3, CsH5CH3SiCl2, CsH5(CH3)2SiC1, ClzCsHzSiCls, Cl7C12I-I2SiCl3, BraCeHsSiCls, and the like or mixtures thereof, to obtain the defined copolymers. The preparation of copolymers of the above type is disclosed in greater detail in the copending application of Fletcher and Hunter, Serial No. 115,783, filed September 14, 1949, and assigned to the assignee of the present invention. The halogenated arylsilanehalides may be prepared by direct halogenation, for example, by the direct chlorination or bromination of CsHsSiXs or CeH5CsI-I4SiX3 in the presence of FeCl3 as a catalyst. Silanes of the formula ClCGH lCHSSlClZ may be prepared, for example, by the reaction of CsHsCl and CHaSiHClz in the presence of BCl as a catalyst at a temperature of 150 to 310 C., as described in U. S. Patent No. 2,499,561.

Silicon having no organic substituents attached thereto may also be incorporated in the copolymer by including material such as SiCl4 or Si(OCzH5)4 in the mixture of silanes to be hydrolyzed.

Thus, it can be seen that the polymeric organosiloxane employed as a reactant in the present invention can contain, along with the units of the general formula units of the general formula where R is an alkyl, aryl, or halogenated aryl radical and may be the same or different radicals, and n is an integer of from O to 3 inclusive, preferably from 1 to 3. The copolymer may be either a fluid or a resinous material. If resinous in nature, the polymeric reactant should be soluble in some inert solvent such as benzene or toluene.

Reaction takes place between the RCH3SiX2, the

polymeric units, and the alkali metal to produce the alkali metal salt and a copolymer containing SiOSi and SiCsI-IaSi types of linkages. When the RCHaSiXz is present in a substantial amount, Si-Si linkages are also formed in the copolymer. Thus novel copolymers may be produced containing all three of the above types of linkages.

These copolymers contain polymeric units of the general formulaeand" I The-relative proportions ofthe-reactantsv are, nt critical; andiany'ratiornay. be employed; Ordinarily, however, the molar ratio-employed of'RCH3S1X2 to XotHi oHi)=si0 units ranges fromabout 20.to 1 to about 0.05 to 1, and theproduct obtained; can. be ,varied .from aresinous type to a fluid type. anywhere :within that range,

The, amount of,-alkali .metal employedis also not critical, but it does controlthe amount of phenylene linke ages orsi silinkageobtained in the product. Amounts of alkalimetal equivalent, to, or. slightlyv in excess of, the totalhalogen present should be used to obtain the maximum amountbf p henylene andiSi-Silinkagespossible in a given system.' Any lesser amount can be employed, however, 'rcsultingin a' comparatively smaller amount of 'suchlinkages in the system and consequently larger amounts of unreacted halogen.

liorexample, when a large molar excess ofiRCl-I3S1X2 ispresent andat least enough of the. alkalimetal is used to be equivalent, to all of the halogen present 111 the system, a copolymeric siloxane is obtained whichcon: tains relatively large amountsof Si-Silinkagesandrelatively smalla'n ounts ofphenylenelinkages. If smaller arnounts of jthe alkali'metal are used, less Si-Si linkages are produced and a quantity of unreacted RCH3SiX2 may remain in the system, or, polymeric units end-blocked a with SiRCH3Cl rnay be obtained, which can be converted by hydrolysis to a. siioxane type-,of unit When a comparative excess of units are present in the system, a vdifierent.type.,of polymer is produced. If this excess is large enough, there may be little or no Si-Si linkages:produced, and the copolymer may contain only SiiOSi and SiCGH lSi types of linkages. In this type of a reaction, it is preferred that the allgalimetal be employed in an,arnount about equivalent to, the RCH3SiX2.

Thelattentype of reaction has .been found particularly useful in increasing theviscosity offluid siloxane'copoly; mers containing Xz'csHs'siOs i units. lt'hasibeen-found extremely ditficult to prepare higher viscosity copolymers containing, for example, (CHz)2SiO, (CH3)aSiO1 z,-and X2CsH3SiOs z units. Such copolymers are veryirnportant as lubricants, and a range of viscosities is highly desirable. The X2Csl-ls radical.attached to S1, however, does not react with the alkali metal. Hence it is possible to incorporate XCsH4SiO3 2 or XC6H4CH3SIO units in the above copolymer, andreact the copolymer with RCH3SiX2' and an alkali metal, thus producin-g- -a ient temperature, but it is preferred to operate at about themelting-point of" the alkali metal in" order to speed up the reaction. Thus, if a diluent is employed, it is preferable that it have a boiling point high enough to allow the alkali metal to melt, thus avoiding any necessity for operating under pressure. Reaction rates at lower temperatures. may be speeded up by using. the alkali metal; in a finely divided form.

Resinous copolymers prepared in: accordanceherewith are of utility as electrical insulating varnishes, laminating resins, protective coatings, water repellents, and the like. Fluids prepared. in accordance herewith are useful as lubricating fluids, hydraulic fluids, damping fluids, etc.

The following examples are illustrative. only. All parts given are parts by'weight.

Example 1 A quantity of ClC6H4CH3SlCl2 was reacted with an excessamount, of ethanolqand the; reaction product dis tilled, yielding theqpureg product: ClCaHrCHsSKOCzl-ls) 2.

This. ethoXylated product washydrolyzedby: adding. it. to

refluxing toluene, The: reaction: proceeded without the further; application ofv heat. When the. addition was complete, the reaction product was refluxed for; two hours and then 22 partschlorobenzene were added to kill oft. the excess sodium. The reaction mixture was cooledto 809' C. and then dumped into 1600 parts ofhot. water; A white powder resulted that was insoluble in toluene. The reactionv product was divided into two portions by filtering'oifv the; white: powder. The filtrate consisted ofa: toluene layer" and a water layer. The toluene'layer. was separated,.filtered: and strip distilled towemove a: portion. of the: solvent present, giving a 30 per cent solids solution of-aresinawhich was found to cure to a tack-free condition, after being heated for about 1 hour at 250 C. This resin was tough and remained flexible for more than hours at 250 C. Thisresin-was a, copolymer.containing units-of the general formulae and I l CHa- CH1 CH3 with small; amounts .of units of. thegeneral t formula CH3 CH3 The white powder obtained from theoriginal filtration was washed with water and dried with acetone, giving an insoluble material which was found to have a chloride content of 4.8 per cent-by weight. A portion of this powderrwas molded at a.temp.erature of 250 C. for 30 minutes under a pressureaof 80001 p. s. i. The molded material was very hard, shiny, and marble-like.

Example 2 A mixture of 25.6 parts (0.15 mol) of the polymeric (ClC6H4CH3SlO) preparedin Example 1 and 544 parts (2.85 mols) CsHsCI-lsSi-Clz was added to 138.5 parts sodium (5.85 mols plus 3 per cent excess) in 2000 parts of refluxing toluene. The reaction mass was refluxed for two hours and then 22 parts chlorobenzene added. The reaction product was:filtered and the solid product obtained was washed with-water to remove all salts, giving 21.5 parts of an insoluble material similar to that obtained in Example 1; The-toluene soluble-portion oft the reaction-product:was washed and concentrated to a 31.5 per cent solids solution. This material can be applied to copper wire and cured at 250 C. to give a tough, flexible coating thereon.

Example 3 Example 1 was repeated but the procedure was reversed in that the sodium was added to the mixture of toluene, silane and siloxane. Approximately the same amount of insoluble material was isolated as was obtained in Example 2. The toluene soluble portion of the reaction product was heat bodied for 4 /2 hours at 200 to 210 C. with air bubbling through the mixture. 217.8 parts of toluene soluble resin were obtained, having a chlorine content of 1.83 per cent by weight. A toluene solution of this resin was cured at 250 C., giving a product which remained flexible for more than 100 hours at 250 C. and which showed no thermal cracking after more than 450 hours at 250 C.

Example 4 A quantity of ClCeH4CH3SiC12 was mixed with toluene and hydrolyzed by adding it to an excess of water. The hydrolyzate was refluxed and then the organic layer was separated from the aqueous HCl layer and washed free of acid. Volatiles were stripped 01f, leaving a polymeric material having polymer units of the formula (ClCsH4CH3SiO). This polymer had a viscosityv of 11,080 cks. at 25 C. and a chlorine content of 19.4 per cent by weight. 200 parts of this polymer were mixed with 200 parts toluene and the mixture heated to reflux. A small amount of water was removed by means of a water trap from the refluxing toluene. The refluxing was continued until no more water appeared. After cooling slightly, 9.07 parts of (CH3)2SiCl2 were added, then at reflux, 6.48 parts of sodium were added. After the reaction was apparently complete, the reaction mixture was refluxed for an additional 30 minutes. The reaction mixture was dumped into dilute HCl, then filtered and the toluene layer separated from the aqueous HCl layer. The toluene layer was neutralized by agitating it with CaCOs and was then refiltered and stripped of all volatiles by distilling the material to a pot temperature of 205 C. at a pressure of about 40 mm. Hg 181 parts of a high viscosity residue were obtained. This product had a viscosity of about 110,000 cks. at 25 C.

and a chlorine content of 18.27 per cent by weight.

Example 5 A copolymer was prepared by mixing 5 molar per cent Cl2CsH3SiCl3, 5 molar per cent ClCsH4CHsSiCl2, 5 molar per cent (CH3)3SiCl and 85 molar per cent (CH3)2SiCl2 and hydrolyzing the mixture in an excess of water. The reaction mixture was heated at reflux for several hours and the product layer then separated from the aqueous HCl and washed free of acid. The product was stripped of volatiles to a pot temperature of 265 C. at a pressure of 1 mm. Hg. The residue was found to have a viscosity of 217.7 cks. at 25 C and a chlorine content of 6.65 per cent by weight. 600 parts of this fluid copolymer were mixed with 600 parts of toluene and refluxed to azeotrope out free water. 10.9 parts of (CH3)2SiClz were then added, followed by 7.77 parts of sodium. All of the sodium appeared to have been reacted in 3 hours time. An additional 1 part of (CH3)2SiCl2 was then added and the whole mixture poured into dilute aqueous HCl. The solvent layer was separated and stirred with about 55 parts of CaCOs, then filtered and strip distilled to a pot temperature of 250 C. at about 2 mm. Hg. The resulting fluid had a viscosity of 242.5 cks. at 250 C. and still contained 6.5 per cent by weight chlorine.

Example 6 The procedure of Example 5 was repeated except that 30 parts of (CH3)2SiClz and 19.4 parts of sodium were employed. The reaction product was finished off as in Example 5. The resulting product had a viscosity of 280 cks. at 25 C. and contained 6.16 per cent chlorine by weight.

Example 7 The procedure of Example 5 was repeated except that in place of the (CH3)2SiCl2, 42.5 parts of CsI-IsCHaSiClz were employed and the amount of sodium used was 15.55 parts. The reaction product was finished off as in Example 5, resulting in a fluid which had a viscosity 345.5

cks. at 25 C. and a chlorine content of 6.16 per cent by weight.

Example 8 When Example 5 is repeated, using 13.2 parts of potassium in place of the sodium, the fluidproduct obtained is similar to that obtained in Example 5;

Example 9 When a copolymer is prepared by hydrolyzing a mixture of 5 molar per cent Cl2C6H3SiCl3, 5 molar per cent BrCsHtSiCls, 10 molar per cent (CH3)sSiCl and 80 per cent (CH3)2SiCl2, the viscosity of the resulting fluid is increased by reacting the copolymeric organosiloxane with (CH3)2SiCl2 and sodium as in Example 5.

Example 10 A copolymeric organosiloxane was prepared by cohydrolyzing a mixture of 2 molar per cent heptachloroxenyltrichlorosilane, 5 molar per cent ClCeH4CH3SiClz, 5 molar per cent (CH3)3SiCl and 88 molar per cent (CH3)2SiCl2. The viscosity of this copolymer is materially increased by reacting it, as in Example 5, with (CH3)2SiClz and sodium.

That which is claimed is:

1. The process comprising reacting in liquid phase an organosilane of the general formula RCHzSiXz, in which R is a radical selected from the group consisting of methyl and phenyl radicals and X represents a substituent selected from the group consisting of chlorine and bromine atoms, an organosiloxane polymer containing polymeric units of the general formula XCoHKCHahSiOEZE where x is an integer of from 0 to 1 inclusive, and X is as above defined, and an alkali metal, whereby there is produced an organosiloxane copolymer in which some of the silicon atoms are linked by oxygen atoms and some of the silicon atoms are linked by phenylene radicals.

2. The process of claim 1 in which the alkali metal is selected from the group consisting of sodium and potassum.

3. The process which comprises reacting in liquid phase an organosilane of the general formula RCHaSiClz where R is a radical selected from the group consisting of methyl and phenyl radicals, an organosiloxane polymer containing polymeric units of the general formula ClCoHKCHahSiO i in which x is an integer of from 0 to 1 inclusive, and sodium, whereby there is produced an organosiloxane copolymer in which some of the silicon atoms are linked by oxygen atoms and some of the silicon atoms are linked by phenylene radicals.

4. The process comprising reacting in liquid phase an organosilane of the general formula R(CH3)SiX2 where R is a radical selected from the group consisting of methyl and phenyl radicals and X is a substituent selected from the group consisting of chlorine and bromine atoms, an organosiloxane copolymer containing polymeric units of the general formulae and 2 e a s/2 where x is an integer of from 0 to l inclusive and X is as above defined, and an alkali metal whereby there is produced an organosiloxane copolymer in which some of the silicon atoms are linked by oxygen atoms and some of the silicon atoms are linked by phenylene radicals and in which the X2CsH3SiO3/2 units remain unreacted.

5. The process of claim 4 in which the alkali metal is selected from the group consisting of sodium and potas- Slum.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,258,219 Rochow Oct. 7, 1941 2,507,515 Clark May 16, 1950 

1. THE PROCESS COMPRISING REACTING IN LIQUID PHASE AN ORGANOSILANE OF THE GENERAL FORMULA RCH3S1X2, IN WHICH R IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF METHYL AND PHENYL RADICALS AND X REPRESENTS A SUBSTITUENT SELECTED FROM THE GROUP CONSISTING OF CHLORINE AND BROMINE ATOMS, AN ORGANOSILOXANE POLYMER CONTAINING POLYMERIC UNITS OF THE GENERAL FORMULA 